Acoustic characterization of hydrate formation and decomposition in clay-bearing sediments

Understanding the acoustic characteristics of hydrates in various sediments is crucial for hydrate resource detection and safe and efficient exploitation,as hydrate occurrence patterns vary greatly in different sediments.In this work,sediments with different bentonite contents,water saturations,and types were prepared to investigate the characteristics of P-wave velocity(reflecting the magnitude of hydrate saturation in the sediment)and amplitude(reflecting the degree of hydrate-sediment cementation)during hydrate formation and depressurization.During hydrate formation,the P-wave velocity and amplitude have similar trends.As clay content increases,the P-wave velocity increase rates quickened.On the other hand,the increased rate of P-wave velocity slows down with the increase of water saturation in the clay-bearing sediments.Comparing various types of sediment shows that the water absorption and swelling of bentonite reduce the pore space,speeding up the cementation of the hydrate with the sediment and increasing P-wave velocity at a faster rate.Correspondence between P-wave velocity and hydrate saturation is strongly related to sediment type,clay content,and water saturation.The rapidly decreasing amplitude in the early stage of hydrate depressurization indicates that hydrate in clay-bearing sediments is weakly cemented to the sediments,which is prone to stratigraphic instability.The findings of this study offer guidance for hydrate resource assessments in clay-bearing sediments as well as geologic risk estimations during hydrate mining.

A Comparison Study of Synkinematic Illite Isolation,Quantitative X-ray Powder Diffraction,and K-Ar Dating for Direct Fault Gouge Analyses

K-Ar dating of synkinematic illite is increasingly recognized as a central method to constrain the timing of shallow crustal faulting.Methods of efficient sample preparation and quantitative identification of illite polytypes are critical to acquiring K-Ar isotope data for authigenic clays.In this respect,we compared the commonly used clay size separation method through centrifugation with vacuum filtration technology,showing that the former is prone to extract fractions with finer particle sizes under similar conditions,thus improving the error in the authigenic end-member age.Additionally,we demonstrated that the side-packed mounting method for X-ray diffraction analysis can significantly enhance the randomness in powder samples,thus improving the quantification accuracy compared with the front-packed and back-packed methods.The validity of our quantification method was confirmed by comparing Profex■modeling patterns with a suite of synthetic mixtures of known compositions,yielding an average analytical error of 3%.Dating results of these artificial mixtures and the reference materials indicated that a large range in percentages of detrital illite and a sufficient amount of age data will produce reliable results for ages of both extrapolated end-members.However,if the range is limited,the extrapolated age close to those of datasets is still reliable.

Diversified roles of mineral transformation in controlling hydrocarbon generation process,mechanism,and pattern

Organic matter(OM)is intimately associated with minerals in clay-rich mudstones,leading to widespread organic-mineral interaction during hydrocarbon generation in argillaceous source rocks.What we are concerned is the effects of the different mineral properties on hydrocarbon generation process and mechanism during mineral transformation.In this way,pyrolysis experiments with smectite-octadecanoic acid complexes(Sm-OA and Ex-Sm-OA)were conducted to analyze correlation of mineralogy and pyrolysis behaviors.Based on organicmineral interaction,hydrocarbon generation process was divided into three phases.At 200–300℃,collapse of smectite led to desorption of OM,resulting in high yield of resin and slight increase in saturates.Subsequently,enhanced smectite illitization at 350–450℃was accompanied with large amounts of saturates and a mere gaseous hydrocarbon.Featured by neoformed plagioclase,ankerite,and illite,500C saw plenty of asphaltene and methane-rich gaseous hydrocarbons,revealing cracking reactions of OM.Noteworthy is that saturated and gaseous hydrocarbons in Ex-Sm-OA were considerably more than that in Sm-OA during second and third phases.Quantitative calculation of hydrogen revealed organic hydrogen provided by cross-linking of OM could not balance hydrogen consumed by cracking reactions,but supply of inorganic hydrogen ensured cracking could readily occur and consequently greatly promoted hydrocarbon generation.Further investigating characteristics of mineralogy and pyrolytic products,as well as effects of solid acidity on hydrocarbon generation,we concluded desorption of OM and decarboxylation promoted by Lewis acid were dominated at 200–300C,resulting in lowdegree hydrocarbon generation.While high yield of saturated and gaseous hydrocarbons in second and third phases,together with occurrence of ankerite,indicated predominance of decarboxylation and hydrogenation promoted by Lewis and Brønsted acid,respectively.Variations in organic-mineral interactions indicated(1)the controls of mineral transformation on hydrocarbon generation process and mechanism include desorption,decarboxylation,and hydrogenation reactions;(2)clay minerals acted as reactants evolving together with OM rather than catalysts.These findings are profoundly significant for understanding the hydrocarbon generation mechanisms,organic-inorganic interactions,and carbon cycle.

Diagenesis and Metamorphism of Triassic Flysch Along Profile Zoige-Lushan,Northwest Sichuan,China

We used illite and chlorite crystaHinities, index minerals, mineral assemblages, polytype and domain size of white mica, electron microprobe analysis （EMPA）, b0 geobarometer and chlorite geothermometer to quantify the diagenetic and metamorphic overprint on the Triassic flysch formations in the Songpan-Garze orogen along profile Zoige-Lushan, northwest Sichuan. Two anchizones, two epizones, one diagenetic zone and a transition belt in-between them are defined on the basis of the obtained data. lllite crystallinity correlates strongly with the best mean domain size of mica and moderately with chlorite crystallinity. 2M1 white mica polytype are observed within the epizone whilst 2M1 and 1M polytypes occur in the anchizone and diagenetic zone. Epizonal metamorphism reached maximum temperatures of 370℃±21℃ at low-to intermediate pressure conditions. Clay minerals underwent Ostwald ripening during metamorphism. Rocks from both sides of the Longmenshan fault reveal contrasting degrees of metamorphic overprint： on the northwest side of the Longmenshan fault, epimetamorphic conditions contrast with diagenetic rocks on the southeast side.

Illite Crystallinity Mapping of Very Low Grade Metamorphism of Triassic Metapelites in the Zoigê Area,Western China

X-ray diffraction methods for estimating the metamorphic grade of diagenetic, anchizone and epizone in metapelites are reviewed and applied to samples from a 7000 m＋ borehole in western China and surface samples from the surrounding Zoige area. Kiibler＇s illite crystallinity （IC） measurements provide more consistent results than calculated values of percentage of illite in the I/S mixed layers and percentage of I/S mixed layers. Down-borehole IC values display a typical burial metamorphic relationship between stratigraphic level and IC. A method for preparing very low grade metamorphic maps is described, and isograds plotted on a regional geological map at selected values of IC, delineating a high temperature diagenetic zone, an anchizone, and an epizone. The map shows that IC values are controlled by stratigraphic level in the north of the study area （i.e. burial metamorphism）, and proximity to an igneous intrusive body in the south （i.e. contact metamorphism）.

K-Ar Dating of Authigenic Illites and Its Applications to the Study of Hydrocarbon Charging Histories of Typical Sandstone Reservoirs in Tarim Basin, China

The Tarim Basin in China comprises eight sets of sandstone reservoirs, five of which are investigated in detail in this study. The main purpose of this study is to investigate the hydrocarbon charging histories of reservoirs by applying K-Ar dating of authigenic illites. The ages of authigenic illites from the Lower Silurian bituminous sandstones in the Central Uplift area range from 383.5 to 235.2 Ma, suggesting that the Silurian oil accumulations were formed from the late Caledonian till the late Hercynian. The ages of authigenic illites from the Upper Devonian Donghe Sandstone reservoirs range from 263.8 to 231.3 Ma, indicating that hydrocarbon accumulations within the Donghe sandstone were formed mainly in the late Hercynian. The authigenic illites ages from the Lower Jurassic Yangxia Group sandstones in the Yinan-2 gas reservoir (Yinan-2, Kuqa Depression) range from 28.1 to 23.9 Ma, suggesting that the initial hydrocarbon charging occurred in the Miocene. The ages of the authigenic illites from the Lower Cretaceous sandstones in the Akemomu gas field (Ake-1, Kashi Sag, Southwest Depression) range from 22.6 to 18.8 Ma, indicating a probable early oil accumulation or early migration of hydrocarbon within this area. The illites from the Paleogene sandstones in the Dina-2 gas reservoir (Dina-201, Kuqa Depression) have a detrital origin; they cannot be used to study the hydrocarbon charging histories. The ages of authigenic illites in the underlying Cretaceous sandstones in the same well (Dina-201) range from 25.5 to 15.5 Ma, indicating that hydrocarbon charging in this reservoir probably occurred within the Miocene. This study highlights the potential of applying K-Ar dating of authigenic illites to investigate the timing of hydrocarbon charging histories of the Tarim Basin reservoir sandstones.

Detrital K-feldspar^(40)Ar/^(39)Ar Ages:Source Constraints of the Lower Miocene Sandstones in the Pearl River Mouth Basin,South China Sea

The South China Sea began to outspread in the Oligocene. A great quantity of terraneous detritus was deposited in the northern continental shelf of the sea, mostly in Pearl River Mouth Basin, which constituted the main paleo-Pearl River Delta. The delta developed for a long geological time and formed a superimposed area. Almost all the oil and gas fields of detrital rock reservoir distribute in this delta. Thirty-three oil sandstone core samples in the Zhujiang Formation, lower Miocene （23-16 Ma）, were collected from nine wells. The illite samples with detrital K feldspar （Kfs） separated from these sandstone cores in four sub-structural belts were analysed by the high-precision 40Ar/39Ar laser stepwise heating technique. All 33 illite 40Ar/39Ar data consistently yielded gradually rising age spectra at the low-temperature steps until reaching age plateaus at mid-high temperature steps. The youngest ages corresponding to the beginning steps were interpreted as the hydrocarbon accumulation ages and the plateau ages in mid-high temperature steps as the contributions of the detrital feldspar representing the ages of the granitic parent rocks in the provenances. The ages of the detrital feldspar from the Zhujiang Formation in the four sub-structural belts were different： （1） the late Cretaceous ages in the Lufeng 13 fault structural belt; （2） the late Cretaceous and early Cretaceous-Jurassic ages in the Huizhou 21 buried hill-fault belt; （3） the Jurassic and Triassic ages in the Xijiang 24 buried hill-fault belt; and （4） the early Cretaceous - late Jurassic ages in the Panyu 4 oil area. These detrital feldspar 4~Ar/39Ar ages become younger and younger from west to east, corresponding to the age distribution of the granites in the adjacent Guangdong Province, Southern China.

Anchimetamorphism of the Neoproterozoic and the Lower Paleozoic along the Profile of Yuanguping in Western Hunan Province, China

The Neoproterozoic and Lower Paleozoic along the profile of Yuanguping in western Hunan Province, China underwent anchimetamorphism. The illite crystallinity (IC) of the <2 μm fractions ranges from 0.23-0.34°△2θfor the Neoproterozoic to 0.23-0.35°△A2θ for the Lower Paleozoic (calibrated with the Kisch IC set, Kisch, 1991). This indicates that the metamorphic grade of the Neoproterozoic and Lower Paleozoic is the anchizone. The peak metamorphic temperature is estimated to be 290-210℃. This result does not agree with the greenschist or subgreenschist facies of the Banxi Group, nor with the lower-greenschist facies or sedimentary cover of the Sinian to Lower Paleozoic, as most previous researchers thought. The illite (K-mica) b0 values range from 0.9074 to 0.8963 (nm) for the Neoproterozoic and the Lower Paleozoic. Based on cumulative frequency curves of the illite (K-mica) b0, the peak metamorphic pressure of the Banxi Group was derived to be of a type that is slightly higher than that of the N. New Hampshire low-intermediate pressure type. Most illites occur as the 2M1 polytype and some in the Neoproterozoic as a mixture of the 2M1+1M types. The distributions of coherent scanning domains (CSDs) of illites along the profile, measured with the XRD method, display a lognormal model and spread out with decreasing Kubler Index of IC. It indicates that illites underwent an Ostwald ripening. The post-anchimetamorphic structural movement not only results in a series of faults but also induces the lattice strain in minerals along the faults and hence impacts the illite crystallinity and causes diagenetic samples to occur within the anchizone. Compared with the cases in eastern and central Hunan Province, the Neoproterozoic and Lower Paleozoic rocks in the west underwent a lower-temperature anchimetamorphism with a pressure lower than that in the east and higher than that in the center of Hunan Province.

Very Low-Grade Metamorphism of Clastic Rocks from the Meso-Neoproterozoic and the Paleozoic along the Profile Yueyang-Linxiang in Northeastern Hunan Province and Its Geological Implications

This study uses illite crystallinity,chlorite crystallinity,illite polytypes,the b0 cell-dimension of K-white mica,clay mineral assemblages and mineral geothermo-geobarometers to investigate the overprint of diagenesis and metamorphism on the Meso-Neoproterozoic and the Lower Paleozoic along the profile Yueyang-Linxiang in northeastern Hunan Province,China.Illite crystallinity Kbler index（KI） of the 〈2μm fractions ranges from 0.225 to 0.485°Δ2θ while chlorite crystallinity Arkai index（AI） ranges from 0.244 to 1.500°Δ2θ.This indicates that the Meso-Neoproterozoic and the Lower Paleozoic along the profile Yueyang-Linxiang were overprinted with diagenesis and anchi- to epimetamorphism.Peak metamorphic temperature is estimated with the IV site chlorite geothermometer roughly at 360℃.The b0 cell dimension values of illites（K-mica） range from 0.9002 to 0.9054 nm and,on average,at 0.9030 nm for the Meso-Neoproterozoic.Based on cumulative frequency curves of illite（K-mica） b0 cell dimension,the peak metamorphic pressure of the MesoNeoproterozoic along the profile Yueyang-Linxiang is derived of an intermediate pressure type.Most illites occur in the 2M1 polytype and some of them in a mixture of 2M1＋1M types especially those in the Paleozoic.This result partly agrees with the conclusion of the lower greenschist and greenschist facies of the Lengjiaxi and Banxi Groups.However,it is not agreed with the sedimentary cover from the Sinian to the Lower Paleozoic or from the Banxi Group to the Lower Paleozoic.Crustal thickening due to ＂collision＂ between the Yangtze and Cathaysia blocks led to an increase in the thickness of the Meso-Neoproterozoic to ca.14 km and resulted in a temperature increase in those rocks due to burial.The very low grade to low grade metamorphism overprinting the Meso-Neoproterozoic implies that the so called ＂Chiangnania or Jiangnan orogen＂ was no relative with the ＂Grenvillian orogeney;instead,it might be a continuous amalgamation product between the Yangtze and Cathaysia blocks.

内蒙古东北地区上古生界伊利石研究

内蒙古东北地区上古生界主要是一套泥质岩石,其详细深入的矿物学工作尚不多见。本文利用JSM-6700F场发射电镜及INCA能谱仪,探讨了伊利石在成岩-极低级变质作用过程中的行为。采用D/max-2500 X-射线衍射仪,研究了伊利石的结晶度、多型和b_0值。伊利石结晶度变化于0.28～0.77,除去构造应力对伊利石结晶度指数值的影响,研究区伊利石结晶度指数应>0.34,反映晚古生代地层主体属于晚期成岩带和低级近变质带。伊利石(白云母)多型分三种类型,分别是1M_d型、1M_d+2M_1混合型和2M_1型,是晚期成岩带和低级近变质带的产物。伊利石(白云母)b_0值变化于8.9892A～9.0404A之间,b_0平均值9.0196A,属中压相。

Silurian-Devonian and Jurassic Thermal Events in the Ordos Basin, China: Indications from K-Ar Dating on Illites

In the Ordos basin, two distinct thermal events of different ages have been identified for the first time by means of K-Ar dating combined with illite crystallinity analysis. For the Late Triassic and Late Permian samples, the K-Ar ages of the < 0.2μm fractions (159-173 Ma) reflect an illitization age related to the Yanshanian movement and indicate a short thermal event in the Middle Jurassic; the K-Ar ages of the <2 μm fractions (210-308 Ma) are interpreted as mixed ages of detrital material and authigenic illites. The K-Ar ages of both < 0.2μm and < 2μm fractions of a Middle Cambrian sample (368 Ma and 419 Ma) correspond to the ages of the metamorphism and earliest granite intrusion in the northern Caledonian Qinling fold zone (380-420 Ma) and show a thermal event during Silurian-Devonian time.

The effect of pH on the sorption of gold nanoparticles on illite

Sorption between nanoparticles(NPs)and minerals may critically affect the migration of associated elements as well as the environmental impact of NPs.Since illite is widely present in soil,sediment,and water,we have experimentally investigated the sorption behavior of citrate-coated gold nanoparticles(AuNPs)as model NPs on illite under different pH and mineral mass conditions.We demonstrated that sorption of these negatively charged AuNPs strongly depended on the suspension pH.At pH above 8,which coincided with the apparent point of zero charge(pH 7.9)of our illite sample,only marginal sorption of AuNPs was observed.At pH 3-8,significant sorption of AuNPs on illite was found,with almost complete sorption occurring at more acidic conditions(pH 3-4).TEM observations revealed that sorption took place through the attachment AuNPs on illite edges.At pH 2,AuNPs mostly formed chain-like fused structures and precipitated out of the suspension.Based upon the above pH dependence,residual organic ligand content after sorption,and complementary sorption results with positively charged AuNPs,we conclude that the sorption process is mainly driven by the electrostatic attraction between negatively charged AuNPs and positively charged illite edges,with possible competitive involvement of citrate molecules.We expect that our findings will improve our understanding of NP-mineral interaction and the environmental fate of NPs.

K-Ar Dating of Fault Gouges from the Red River Fault Zone of Vietnam

Constraining the timing of fault zone formation is fundamentally important in terms of geotectonics to understand structural evolution and brittle fault processes.This paper presents the first authigenic illite K-Ar age data from fault gouge samples collected from the Red River Shear Zone at Lao Cai province,Vietnam.The fault gouge samples were separated into three grain-size fractions（〈0.1 μm,0.1-0.4 μm and 0.4-1.0 μm）.The results show that the K-Ar age values decrease from coarser to finer grain fractions（24.1 to 19.2 Ma）,suggesting enrichment in finer fraction of morerecently grown authigenic illites.The timing of the fault movement are the lower intercept ages at 0%detrital illite（19.2 ± 0.92 Ma and 19.4 ± 0.49 Ma）.In combination with previous geochronological data,this result indicates that the metamorphism of the Day Nui Con Voi（DNCV） metamorphic complex took place before ca.26.8 Ma.At about 26.8 Ma-25 Ma,the fault strongly acted to cause the rapid exhumation of the rocks along the Red River-Ailoa Shan Fault Zone（RR-ASFZ）.During brittle deformation,the DNCV slowly uplifted,implying weak movement of the fault.This brittle deformation might have lasted for ca.5 Ma.

Characterization of a Rarely Encountered Sericite with Earthy Luster

A rarely encountered sericite was investigated using X-ray diffraction,differential thermal analysis,and scanning electron microscopy.XRD analysis shows that the pattern of the sericite in the sample is similar to that of illite.DTA (TG) analyses show that only a weak heat absorption reaction takes place at 566℃,which is contributed to the polymorphic transformation of quartz,and no change in mass was detected in the range from ambient temperature to 800℃.These reveal that no water escapes from the crystal structure of the clay mineral during heating and therefore indicated that the clay mineral is obviously sericite in species instead of illite.SEM observations show that the sericite particles are significantly small in size and growth steps and irregular structures develop on the crystal surfaces as well as the colored mineral inclusions,which might suggest some loss of optical properties of the sample and thus lead to the variance,with earthy luster of the aggregate,from typical sericite in optical characters.

Isotopic Ages of the Penglai Group in the Jiaobei Belt and Their Geotectonic Implications

The Penglai Group in the Jiaobei Belt is the only remaining cover of the Archaean to Early Proterozoic crystalline basement in eastern Shandong. The ages of deposition of the Penglai Group and of its deformation and metamorphism have long been a subject of speculation. Whole-rock Rb-Sr ages, illite-whole-rock pair Rb-Sr ages and illite K-Ar ages recently obtained from the Penglai Group slates are reported and interpreted in this paper. On the basis of structural and metamorphic studies coupled with analyses of illite crystallinity, XRD and SEM , a whole-rock age of 473±32 Ma (Ordovician) is interpreted as the time of termination of burial metamorphism experienced by the Penglai Group. Therefore, the age of the Penghai Group is older than Ordovician. The first-phase folding and syntectonic low greenschist facies metamorphism in the Penglai Group, i.e. the Penglai Movement, took place before 299±4 Ma B.P., i.e in the Late Carboniferous. The Penglai Movement that occurred in the Jiaobei Belt on the southern margin of the North China Plate is attributed to collision between the North China and Yangtze plates along the Jiaonan Collision Belt. This demonstrates that the continent-continent collision between the North China and Yangtze plates east of the Tan-Lu Fault Zone took place in the Late Carboniferous. The collision caused N-S compression and deformation in the southern margin belt of the North China Plate north of the Qinling-Dabieshan-Jiaonan Collision Belt.

Diagenesis and Very Low-Grade Metamorphism of the Upper Permian Yangjiagou Formation in Eastern Changchun, China:Evidence from Clay Mineral Geothermobarometers

The metamorphic conditions of the Upper Permian Yangjiagou Formation in eastern Changchun, China, were evaluated based on the mineral assemblage, illite crystallinity, illite polytypism,the b dimension of illite, and the chemical composition of chlorite. The pelitic rocks in the Yangjiagou Formation are characterized by illite + kaolinite + chlorite ± mixed-layer chlorite/smectite and detrital quartz + plagioclase. Illite in the formation has a crystallinity of 0.38-0.55 and comprises mixed 2 Mand1 Mpolytypes, indicating a metamorphic temperature of >200℃. Based on the chemical composition of chlorite and the chlorite geothermometer, we estimated diagenetic to very low-grade metamorphic conditions with temperatures of 185℃～204℃. The b dimension of illite varies from 8.992 A to 9.005 A.We used a mathematical algorithm to extend Guidotti and Sassi’s(1986) diagram relating illite b dimension with temperature and pressure, and used this diagram, together with illite crystallinity and chlorite chemical composition, to semi-quantitatively estimate the formation pressure at<1.2 kbar. These reveal that the Yangjiagou Formation has experienced very low-grade metamorphism.

Displacement of shale gas confined in illite shale by flue gas: A molecular simulation study

The shale gas is an unconventional supplementary energy to traditional fossil energy,and is stored in layered rocks with low permeability and porosity,which leads to the difficulty for exploration of shale gas.Therefore,using CO_(2) gas to displace shale gas has become an important topic.In this work,we use molecular simulations to study the displacement of shale gas by flue gas rather than CO_(2),in which flue gas is modeled as a binary mixture of CO_(2) and N_(2) and the shale model is represented by inorganic Illite and organic methylnaphthalene.CH_(4) is used as a shale gas model.Compared to the pure CO_(2),flue gas is easily available and the cost of displacement by flue gas would become lower.Results indicate that the pore size of shale is an important factor in the process of displacing shale gas and simultaneously sequestrating flue gas,while the flue gas N_(2)-CO_(2) ratio shows a small effect on the process of CH_(4) displacement,because the high partial pressure of flue gas is the main driving force for displacement of shale gas.Moreover,the geological condition also has a significant effect on the process of CH_(4) displacement by flue gas.Therefore,we suggest that the burial depth of 1 km is suitable operation condition for shale gas displacement.It is expected that this work provides a useful guidance for exploitation of shale gas and sequestration of greenhouse gas.

Evaluation of 40^Ar/39^Ar Geochronology of Authigenic Illites in Determining Hydrocarbon Charge Timing： A Case Study from the Silurian Bituminous Sandstone Reservoirs, Tarim Basin, China

The Silurian bituminous sandstones（SBS） in the Tarim Basin, China are important basinwide reservoirs with an estimated area of approximately 249000 km^2. We investigated the ages of authigenic illites in the SBS reservoirs and constrained their formation timing by using the 40^Ar/39^Ar step wise heating method. The age spectra, 39^Ar recoil loss and their controlling factors were investigated systematically. The 40^Ar/39^Ar ages were compared with the conventional K/Ar ages of identical clay fractions. The clay in the SBS reservoirs is dominated by orderly mixed-layer illite/smectite（I/S） with 5%–30% smectite layers. The I/S minerals morphology comprises primarily honeycomb, short filamentous and curved-lath particles, characteristic of authigenic illites. The unencapsulated 40^Ar/39^Ar total gas ages（UTGA） of the authigenic illites range from 188.56 ± 6.20 Ma to 491.86 ± 27.68 Ma, which are 7% to 103% older than the corresponding K/Ar ages of 124.87 ± 1.11 Ma to 383.45 ± 2.80 Ma, respectively. The K-Ar ages indicate multistage accumulations with distinct distribution patterns in the Tarim Basin： older（late Caledonian-early Hercynian） around the basin margin, younger（late Hercynian） in the basin centre, and the youngest（middle to late Yanshanian） in the Ha-6 well-block, central area of the North Uplift. The age difference is believed to have been caused by the 39^Ar recoil loss during the irradiation process. Compared with the K/Ar ages, the estimated 39^Ar recoil losses in this study are in the range from 7% to 51%. The 39^Ar recoil loss appears to increase not only with the decreasing particle sizes of the I/S, but also with increasing percentage of smectite layers（IR） of the I/S, and smectite layer content（SLC） of the samples. We conclude that due to significant 39^Ar recoil losses, UTGA may not offer any meaningful geological ages of the authigenic illite formation in the SBS and thus can not be used to represent the hydrocarbon charge timing. 39^Ar recoil losses during 40^Ar/39^Ar dating can not be neglected when dating fine authigenic illite, especially when the ordered mixed-layer I/S containing small amount of smectite layers（IR30%） in the reservoir formations. Compared with the unencapsulated Ar-Ar method, the conventional K-Ar method is less complicated, more accurate and reliable in dating authigenic illites in petroleum reservoirs.

Fracture development and hydrocarbon accumulation in tight sandstone reservoirs of the Paleogene Huagang Formation in the central reversal tectonic belt of the Xihu Sag, East China Sea

By using thin section identification, cathodoluminescence, major and trace elements and fluid inclusion tests and authigenic illite dating, based on observation of core cracks, combined with the microscopic characteristics and imaging logging characteristics of fractures, the stages of the fractures in the Huagang Formation of the central reversal tectonic belt of the Xihu Sag in the East China Sea, and the matching relationship between the fracture development stages and the oil and gas charging stages are clarified. There are diagenetic fractures and tectonic fractures in the reservoirs of the Huagang Formation in the study area. The diagenetic fractures developed during the diagenetic stage of the reservoirs and have less effect on oil and gas migration and transport. The tectonic fractures are divided into three stages based on tectonic movements controlling the fractures and their relationships with hydrocarbon charging: The first stage of fractures was generated in the early stage of the Himalayan Movement–Longjing Movement(12–13 Ma ago), when the tectonic stress caused the sutures and shale strips to twist, deform, and break. Tectonic microfractures generated in this period had short extension, narrow width, and poor effectiveness, and had little effect on oil and gas migration and transport. The second stage of fractures came up during the middle-late period of Himalayan Movement–Longjing Movement(9–12 Ma ago), when tectonic movements caused the development of tectonic fractures in the central reversal tectonic belt, these fractures are of large scale, long extension, and good effectiveness, and matched with the first stage of large scale oil and gas charging(9–12 Ma ago), so they play an important role in oil and gas migration, transportation, and accumulation. The third stage of fractures were created from Himalayan Movement–Okinawa Trough movement to the present day(0–3 Ma ago), the fractures are tectonic ones developing successively;matching with the second stage(0–3 Ma ago) of large-scale oil and gas charging, they created conditions for continuous natural gas migration and transportation. All these prove that the development of reservoir fractures in the Huagang Formation of Xihu Sag can provide seepage space and continuous and effective channels for efficient migration and accumulation of oil and gas.

Adsorption of Pentachlorophenol onto Oxide and Clay Minerals: Surface Reaction Model and Environmental Implications

The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.